Descripción: New insights into equilibrium and dynamical aspects of electron photodetachment reactions in small water clusters were given. It focuses on assessing the effects of thermal and polarization fluctuations provided by three cluster environments with different extents of spatial confinement, on the microscopic mechanisms that drive the reaction. These fluctuations, in turn, determine the characteristics of the electron localization and the subsequent detachment following photoexcitation of the probe.

Descripción: We have calculated the electrical conductivity in the current-in-plane geometry of multilayered granular alloys composed of Co clusters embedded in Ag alternating with pure Ag layers. In particular, we have paid attention to the conductivity behavior as a function of Ag layer thickness, Co clusters' size, and degree of percolation. The electronic structure is self-consistently calculated within the unrestricted Hartree-Fock approximation using a parametrized tight binding Hamiltonian which includes a Hubbard-like term. The conductivity tensor is obtained by using the semiclassical Boltzmann equation in the anisotropic relaxation time approximation. We have used a s-d Mott-like scattering model for the electronic mean free path taking into account the Sondheimer's picture for electronic transport in thin films. We find that the experimental conductivity behavior at coalescence can be explained through the electronic band contribution. The conductivity behavior of continuous multilayers is already attained in the very early stage of percolation, as in the experiments. © 2007 American Institute of Physics.

Descripción: A novel method for simulating the statistical mechanics of molecular systems in which both nuclear and electronic degrees of freedom are treated quantum mechanically is presented. The scheme combines a path integral description of the nuclear variables with a first-principles adiabatic description of the electronic structure. The electronic problem is solved for the ground state within a density functional approach, with the electronic orbitals expanded in a localized (Gaussian) basis set. The discretized path integral is computed by a METROPOLIS Monte Carlo sampling technique on the normal modes of the isomorphic ring polymer. An effective short-time action correct to order τ4 is used. The validity and performance of the method are tested by studying two small lithium clusters, namely Li4 and Li5+. Structural and electronic properties computed within this fully quantum-mechanical scheme are presented and compared to those obtained within the classical nuclei approximation. Quantum delocalization effects turn out to be significant as shown by the fact that quantum simulation results at 50 K approximately correspond to those of classical simulations carried out at 150 K. The scaling factor depends, however, on the specific physical property, thus evidencing the different character of quantum and thermal correlations. Tunneling turns out to be irrelevant in the temperature range investigated (50-200 K). © 1998 American Institute of Physics.

Descripción: The effect of O2+, H2+ O 2+, and N2+ O2 + ion-beam irradiation of carbon nanotubes (CNTs) films on the chemical and electronic properties of the material is reported. The CNTs were grown by the chemical vapor deposition technique (CVD) on silicon TiN coated substrates previously decorated with Ni particles. The Ni decoration and TiN coating were successively deposited by ion-beam assisted deposition (IBAD) and afterwards the nanotubes were grown. The whole deposition procedure was performed in situ as well as the study of the effect of ion-beam irradiation on the CNTs by x-ray photoelectron spectroscopy (XPS). Raman scattering, field-effect emission gun scanning electron microscopy (FEG-SEM), and field emission (FE) measurements were performed ex situ. The experimental data show that: (a) the presence of either H2+ or N2 + ions in the irradiation beam determines the oxygen concentration remaining in the samples as well as the studied structural characteristics; (b) due to the experimental conditions used in the study, no morphological changes have been observed after irradiation of the CNTs; (c) the FE experiments indicate that the electron emission from the CNTs follows the Fowler-Nordheim model, and it is dependent on the oxygen concentration remaining in the samples; and (d) in association with FE results, the XPS data suggest that the formation of terminal quinone groups decreases the CNTs work function of the material. © 2011 American Institute of Physics.

Descripción: Aims: To study the modification of the cell wall of Lactobacillus casei ATCC 393 grown in high salt conditions. Methods and Results: Differences in the overall structure of cell wall between growth in high salt (MRS + 1 mol l -1 NaCl; N condition) and control (MRS; C condition) conditions were determined by transmission electronic microscopy and analytical procedures. Lactobacillus casei cells grown in N condition were significantly larger than cells grown under unstressed C condition. Increased sensitivity to mutanolysin and antibiotics with target in the cell wall was observed in N condition. Purified cell wall also showed the increased sensitivity to lysis by mutanolysin. Analysis of peptidoglycan (PG) from stressed cells showed that modification was at the structural level in accordance with a decreased PG cross-link involving penicillin-binding proteins (PBP). Nine PBP were first described in this species and these proteins were expressed in low percentages or presented a modified pattern of saturation with penicillin G (Pen G) during growth in high salt. Three of the essential PBP were fully saturated in N condition at lower Pen G concentrations than in C condition, suggesting differences in functionality in vivo. Conclusions: The results show that growth in high salt modified the structural properties of the cell wall. Significance and Impact of Study: Advances in understanding the adaptation to high osmolarity, in particular those involving sensitivity to lysis of lactic acid bacteria.